TW202248349A - Long-chain alkyl polyphenyl ether resin composition and application thereof - Google Patents

Abstract

The invention provides a long-chain alkyl polyphenyl ether epoxy resin composition and application thereof, and relates to the technical field of high polymer materials. The long-chain alkyl polyphenyl ether resin composition comprises the following raw materials in parts by weight: 100 parts of epoxy resin, 20-60 parts of long-chain alkyl polyphenyl ether, 80-100 parts of bismaleimide resin and 40-80 parts of a hardening agent. The structure of the long-chain alkyl polyphenyl ether is shown as a formula I, R1-C-R2 is C8-C25 alkyl, m+n is 10-40, and the number-average molecular weight Mn is 1500-6000. A laminated plate prepared from the long-chain polyphenyl ether resin composition has the advantages of high moisture resistance, good heat resistance, good structural stability, excellent toughness, low dielectric constant, low dissipation factor, low expansion coefficient, low raw material cost and the like.

Description

Long chain alkyl polyphenylene ether resin composition and its application

The invention relates to the technical field of polymer materials, in particular to a long-chain alkyl polyphenylene ether resin composition and its application.

A printed circuit board (PCB) is a circuit substrate of an electronic device, which carries other electronic components and electrically connects these components to provide a stable circuit working environment. Common printed circuit boards are copper clad laminates (CCL), which are mainly composed of resin, reinforcing material and copper foil. Common resins such as epoxy resin, phenolic resin, polyamine formaldehyde, cyanide Ester, bismaleimide, hydrocarbon resin and Teflon, etc., and commonly used reinforcing materials such as glass fiber cloth, glass fiber mat, insulating paper, etc.

Considering the back-end electronic processing formula, heat resistance, dimensional stability, chemical stability, processability, toughness and mechanical strength and other properties must be considered when making printed circuit boards. Generally speaking, printed circuit boards made of epoxy resin can have the above-mentioned characteristics, so it is the most commonly used resin in the industry. However, printed circuit boards made of epoxy resin often have relatively high dielectric constant (dielectric constant, Dk) and dissipation factor (dissipation factor, Df), in which the transmission rate of the signal is roughly inversely proportional to the square root of Dk, so A high Dk tends to slow down the signal transmission rate of the laminated board; while Df is related to the signal transmission quality, the higher the Df, the greater the proportion of the signal lost in the laminated board material due to material impedance. Therefore, how to provide laminates with good physical and chemical properties and low Dk and Df has been a subject of research and development in the industry.

Polyphenylene ether resin (polyphenylene ether resin or polyphenylene oxide resin, referred to as PPE resin or PPO resin) has gradually become an ideal material for high-frequency and low-dielectric printed circuit boards due to its low dielectric constant and low dielectric loss. . However, the existing polyphenylene ether cannot meet the requirements of the printed circuit board industry in some characteristics, such as the electrical characteristics after high temperature and high humidity.

In order to solve this problem, the applicant once proposed a polyphenylene ether epoxy resin composition (application number 201911213245.1), which has good electrical and structural properties. The present invention is an improvement made on the basis of the patent application. By improving the structure of polyphenylene ether, the properties of the polyphenylene ether resin composition such as moisture resistance, heat resistance, adhesion, and thermal expansion coefficient are optimized, and at the same time, the product is reduced. production cost.

Based on this, it is necessary to address the above problems and provide a long-chain alkyl polyphenylene ether resin composition, which has the advantages of moisture resistance, heat resistance, good adhesion, and low thermal expansion coefficient when applied to the production of laminated boards.

The long-chain alkyl polyphenylene ether resin composition provided by the present invention includes the following raw materials in parts by weight:

epoxy resin 100 parts,

Long chain alkyl polyphenylene ether 20~60 parts,

Bismaleimide resin 80~100 parts,

Hardener 40~80 parts;

式I The structure of the long-chain alkyl polyphenylene ether is shown in formula I:

Formula I

Wherein, R ₁ -CR ₂ is a C8~C25 alkyl group, m+n=10~40, and the number average molecular weight Mn is 1500~6000.

The above-mentioned long-chain alkyl polyphenylene ether resin composition can improve the moisture resistance, heat resistance and adhesiveness of the epoxy resin composition by selecting the raw materials and the proportion, especially can greatly reduce the coefficient of thermal expansion and improve the structure. stability. Moreover, the long-chain alkyl polyphenylene ether used in the present invention has good solvent selectivity, such as good solubility in solvents such as benzenes, ketones, amides, pyridine, etc., making the long-chain alkyl polyphenylene ether The phenylene ether resin composition also has better solvent selectivity.

Among them, the addition amount of long-chain alkyl polyphenylene ether is preferably 20-60 parts by weight, and when it is lower than 20 parts by weight, the advantages that the long-chain alkyl polyphenylene ether derivative of the manufactured laminate can contribute cannot be shown, When it exceeds 60 parts by weight, the structural toughness becomes poor. Moreover, when the R ₁ -CR ₂ long-chain alkyl is less than C7 or the polymerization amount is less than 10, the laminated sheet cannot exhibit the low water absorption or electrical properties provided by the long-chain alkyl or polyphenylene ether. When R ₁ -CR _2. When the long-chain alkyl group is greater than C25 or the polymerization amount is greater than 50, the resin is easy to polymerize and agglomerate, which will also affect the structure of the produced board, which is easy to be brittle and cracked, and the appearance of the finished product is poor.

In one of the embodiments, the epoxy resin is selected from one of: brominated bisphenol A epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, and phosphorus-containing epoxy resin or two or more.

In one embodiment, the bismaleimide resin is selected from: 4,4'-diphenylmethane bismaleimide, bismaleimide toluene, diethylbismaleimide Amine toluene, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4 '-Diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4- Trimethyl)hexane, 2,3-dimethylphenylmaleimide, 2,6-dimethylphenylmaleimide, N-phenylmaleimide, containing aliphatic long chain structure One or two or more of the maleimides. The maleimide resin can also be a prepolymer of the above compounds, for example: a prepolymer of a diallyl compound and a maleimide compound, a prepolymer of a diamine and a maleimide compound , a prepolymer of a polyfunctional amine and a maleimide compound, or a prepolymer of an acidic phenol compound and a maleimide compound, and the like.

In one of the embodiments, the maleimide resin is selected from: trade names BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, Maleimide resins such as BMI-4000, BMI-4000H, BMI-5000, BMI-5100, BMI-7000 and BMI-7000H are produced by Daiwakasei Company, or trade names BMI-70, BMI-80 etc. are produced by K.I Chemicals The maleimide resin produced by the company, or the maleimide resin produced by Evonik Chemical Company with trade names Compimide MDAB, Compimide TDAB, Compimide DE-TDAB, etc.

In one of the embodiments, the maleimide resin containing aliphatic long chain structure is selected from: trade names BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI- Maleimide resins such as 3000J, BMI-3000G, BMI-3000GE, BMI-5000 and BMI-6000 produced by Designer Molecular Company.

The dosage of bismaleimide resin is preferably 80-100 parts by weight; where the dosage is less than 80 parts by weight, the chemical and electrical properties of bismaleimide resin and long-chain alkyl polyphenylene ether cannot be exhibited , the dosage is higher than 110 parts by weight, and the structure of the formed laminate is poor, the appearance is poor, the flatness is poor, and it is easy to be brittle.

In one of the embodiments, the amount of bismaleimide resin is 80-90 parts. If the bismaleimide resin exceeds 90%, the toughness of the laminate may be deteriorated. At the same time, a small amount of bismaleimide resin is also beneficial to reduce the production cost of the product.

In one embodiment, the hardener is selected from one or both of diamino diphenyl sulfone (DDS for short) and amino triazine phenolic resin. The above-mentioned hardener can react with the functional groups in the epoxy resin molecules to form an interpenetrating network epoxy composite material. The hardening agent is preferably 40-80 parts by weight. The dosage is less than 40 parts by weight, poor reactivity, poor structure, poor heat resistance and other physical properties, if the weight part is more than 100 parts by weight, too fast reaction is not conducive to the process operation, and the molding appearance defect rate of the laminate is easy to increase.

In one of the embodiments, 130-170 parts of solvent and 30-35 parts of functional additives are also included.

In one embodiment, the solvent is selected from: toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, methyl ethyl ketone, acetone, xylene, methyl isobutyl ketone, N,N-dimethylformaldehyde One or more of amide, N,N-dimethylacetamide, and N-methylpyrrolidone.

In one embodiment, the functional additive is selected from one or more of fillers, flame retardants, hardening accelerators, dispersants, and tougheners.

In one of the embodiments, the hardening accelerator is selected from: 2-methylimidazole (2-Methyl-Imidazole, 2MI), 2-ethyl-4-methylimidazole (2-Ethyl-4-Methyl-Imidazole , 2E4MI) and 2-phenylimidazole (2-Phenyl-Imidazole, 2PI) in one or more. The above curing accelerator can accelerate the curing time of the prepreg.

In one of the embodiments, the R ₁ is a C6-C12 long-chain alkyl group, and the R ₂ is hydrogen or a C1-C12 alkyl group.

It can be understood that a long-chain alkyl group is an alkyl group that does not contain a straight chain.

In one of the embodiments, the R ₁ is a C9 or C11 long-chain alkyl group, and the R ₂ is hydrogen or a C11 long-chain alkyl group; m+n=24~35 of the long-chain alkyl polyphenylene ether , the number average molecular weight Mn is 3300~4000. Long-chain polyphenylene ethers satisfying this condition have better properties, such as lower thermal expansion coefficient and Z-axis expansion rate, and have better toughness at the same time.

In one of the embodiments, m+n=24~27, and the number average molecular weight Mn is 3500~4000.

In one of the embodiments, the R ₁ is a C9 long-chain alkyl group, and the R ₂ is hydrogen.

In one embodiment, the R ₁ is a C11 long-chain alkyl group, and the R ₂ is a C11 long-chain alkyl group.

In one embodiment, the R ₁ is a C9 or C11 long-chain alkyl group, and the R ₂ is hydrogen or a C11 long-chain alkyl group.

In one of the embodiments, the long-chain alkyl polyphenylene ether tree is prepared by the following method:

S1, using C8~C25 alkyl ketone and 2,6-dimethylphenol as raw materials, adding an acid catalyst, and reacting to obtain a precursor; the acid catalyst is mercaptopropionic acid and sulfuric acid, or trifluoromethanesulfonic acid and sulfuric acid;

S2. Mix the precursor, metal catalyst, dimethylbutylamine and solvent to obtain a pre-reaction solution; dissolve 2,6-dimethylphenol in the solvent to obtain a 2,6-dimethylphenol solution; The reaction solution is mixed with 2,6-dimethylphenol solution, and reacted to obtain long-chain alkyl polyphenylene ether.

（式II）。 Among them, the structure of the precursor (long-chain alkyl dimethyl bisphenol) is shown in the following formula II:

(Formula II).

（式III） The reaction formula of step S2 is shown in formula III:

(Formula III)

In the above preparation method, a mixture of trifluoromethanesulfonic acid and sulfuric acid is used as a catalyst in the preparation of the precursor (long-chain alkyl dimethyl bisphenol), which can increase the yield of the precursor to 50%, or even as high as 75%. Above, when the catalyst is only sulfuric acid, the yield of the precursor is lower than 30%. The precursor is the key raw material for the preparation of long-chain polyphenylene ether. The yield of the precursor is greatly increased, which can greatly reduce the production rate of long-chain alkanes. The production cost of polyphenylene ether.

In the step of synthesizing long-chain polyphenylene ether, the metal catalyst and dimethylbutylamine (DMBA) are used in the present invention, which is different from the metal catalyst and triethylamine commonly used in the general method. The inventors found that the long-chain alkyl dimethyl bisphenol has low reactivity with triethylamine, and dimethylbutylamine was specially selected after passing the test. The inventors also found that the molar ratio of dimethylbutylamine to metal catalyst (such as copper ion halide) is (20-35): 1, the reaction effect is better, more preferably (25-30): 1, when two When the ratio is lower than 20:1, the copper ion halide is easy to precipitate, the dissolution is not complete, and the reaction is unstable. When the ratio is higher than 35:1, side reactions are likely to occur and affect product quality.

In one embodiment, the acid catalyst is mercaptopropionic acid and sulfuric acid with a mass ratio of (2-4):1, or trifluoromethanesulfonic acid and sulfuric acid with a mass ratio of (2-4):1. Described sulfuric acid is concentrated sulfuric acid.

In one embodiment, in the step S1, the molar ratio of C8~C25 alkyl ketones to 2,6-dimethylphenol is (3~5):1, the reaction temperature is 70~150°C, and the reaction time is 10~14 hours.

When the molar ratio of C8~C25 alkyl ketone and 2,6-dimethylphenol is lower than 3:1, the excess of 2,6-dimethylphenol reactant will cause waste of raw materials; when the molar ratio is higher than 5:1 , the reaction is not complete, and only long-chain alkyl monophenol structures may be formed.

More preferably, the molar ratio of C8~C25 alkyl ketones to 2,6-dimethylphenol is 4:1.

In one embodiment, the metal catalyst is selected from one or more of copper bromide, copper chloride, cuprous bromide, cuprous chloride, cupric oxide and cuprous oxide.

In one of the embodiments, the step S1 also includes the purification of the product: dissolving the product with ether, neutralizing and extracting with saturated aqueous sodium bicarbonate solution, taking the organic phase, and extracting with deionized water until the pH is 5~ 6. Concentrate the organic phase, add methanol solution (the volume ratio of water and methanol is 1:3) and place it at 0~4 °C to crystallize the product, filter and retain the solid to obtain a pure precursor.

In one of the embodiments, in the step S2, the molar ratio of the precursor to dimethylbutylamine is 1: (5~8), and the molar ratio of the metal catalyst to dimethylbutylamine is 1: (25~ 30), the molar ratio of precursor to 2,6-dimethylphenol is 1: (8~12), and the reaction is carried out under the ambient condition of oxygen.

In one embodiment, in the step S2, the reaction temperature is 30-40°C.

In one of the embodiments, the step S2 also includes the purification of the product: add EDTA aqueous solution to the product to remove metal ions, add hydrochloric acid for neutralization, take the organic layer, add methanol solution for extraction, and extract at a speed above 3000 rpm Stir to force the solid to precipitate, take the solid, and dry it to obtain the long-chain polyphenylene ether.

The present invention also provides a prepreg, which is prepared from raw materials including the long-chain alkyl polyphenylene ether resin composition.

The present invention also provides an application of the above-mentioned long-chain alkyl polyphenylene ether resin composition or the above-mentioned prepreg in the preparation of laminated boards.

The present invention also provides a method for preparing a laminate, comprising the following steps:

Preparation of a prepreg: coating the above-mentioned long-chain alkyl polyphenylene ether resin composition on a glass fiber cloth and drying to obtain a prepreg;

Hot pressing: Laminate several prepregs, laminate copper foil on both sides of the laminate, and heat press to obtain a copper foil-coated laminate.

Compared with the prior art, the present invention has the following beneficial effects:

The long-chain alkyl polyphenylene ether epoxy resin composition of the present invention has the advantages of good moisture resistance, heat resistance and adhesion, low thermal expansion coefficient, good structural stability and the like. The above epoxy resin composition is applied to the preparation of epoxy resin and electronic laminate, and has the advantages of strong hydrophobicity, good heat resistance, good structural stability, good toughness, low dielectric constant, low dissipation factor, low expansion coefficient, and the like.

In order to facilitate the understanding of the present invention, preferred embodiments will be given below to describe the present invention more fully. However, the present invention can be embodied in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the invention. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the following examples and comparative examples, unless otherwise specified, the raw materials are all commercially available or prepared by conventional methods.

Example 1

1. Preparation of precursor

Add 57.3 g of 2,6-dimethylphenol and 18.56 g of decanal (i.e., decanal or n-decyl aldehyde) into a 500 mL four-neck flask. The reflux condensation temperature is controlled at 0 °C, and the catalyst (3 g of mercapto propionic acid and 1 g sulfuric acid), the reaction temperature was controlled at 80 °C, and the reaction time was 12 h. After the reaction was completed, the product was dissolved with ether, neutralized and extracted with saturated aqueous sodium bicarbonate solution, and the organic layer was kept, and extracted with deionized water until the pH was 5-6. Concentrate the organic layer, add methanol solution (the volume ratio of deionized water to methanol is 1:3), mix and put it in a refrigerator at 4 °C for crystallization, and filter the precipitated product to obtain precursor X1, about 34.08 g of the product. The rate is 75%.

（式IV）。 The structure of the precursor X1 is shown in Formula IV, with a relative molecular mass of 382.5.

(Formula IV).

2. Preparation of long chain alkyl polyphenylene ether

Set up a 5 L four-neck round bottom bottle, install a mechanical stirrer, a thermometer, an oxygen supply tube, and an addition funnel, set the stirring speed at 150–200 rpm, add 1.3 L toluene, 20 g CuCl ₂ and 420 g DiCl 2 _{Methylbutylamine} , the molar ratio of CuCl2 to dimethylbutylamine is 1:28, and oxygen is fed into the mixture for 30 min to continue stirring. Then add 251 g of precursor X1 and wait until it is completely dissolved.

Dissolve 800 g of 2,6-dimethylphenol (the molar ratio of 2,6-dimethylphenol to precursor X1 is 10:1) in 1 L of toluene, pour the 2,6-dimethylphenol solution Put it into the addition funnel, slowly drop it into the round bottom bottle, stir and react at 35 °C for 11~14 h, stop feeding oxygen after the reaction is completed.

（式V） The product was transferred to a 12 L round bottom bottle, poured into 820 ml of 0.1 mol/L EDTA aqueous solution, stirred at room temperature for 6 h, heated to 50-60 °C, and continued to stir for 2 h. Collect the upper toluene layer solution, put it into a round bottom bottle, and add 2.4 L of 1% hydrochloric acid solution. Collect the toluene layer solution, stir for 2 h, and let stand for 24 h. Collect the toluene layer solution, pour it into 10 L of methanol solution, and precipitate a large amount of precipitated products, keep stirring at room temperature for at least 1 h, filter and dry in a vacuum oven (120 °C, 16 h) to obtain long-chain polyphenylene ether A1 , whose structure is shown in Formula V.

(Formula V)

60% of the components in long-chain polyphenylene ether A1 are long-chain polyphenylene ethers with m+n=25~27 and molecular weight Mn=3382~3623. The product is a light yellow powder, which has good solubility in solvents such as benzene, ketones, amides, and pyridine. The infrared spectrum of the product was tested by an infrared spectrometer (model: FTS-3000) of Bio-RAD Company, and the results are shown in Fig. 1 .

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition C1.

4. Preparation of laminates

Coat resin composition C1 on 7628 glass fiber cloth with a roll coater, adjust the impregnation amount of resin and glass fiber cloth to 43%, then place it in a dryer, heat and dry at 180 °C for 2-5 min, A prepreg in a semi-hardened state was produced, and then eight sheets of prepreg were laminated with a 1-ounce copper foil on each of the outermost layers on both sides. This was then hot-pressed to obtain a copper foil-coated laminate D1. Among them, the hot pressing conditions are: heating up to 200 °C at a heating rate of 2.0 °C/min, and hot pressing at 200 °C with a total pressure of 25 kg/cm2 (initial pressure of 12 kg/cm2) for 90 min.

Example 2

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

It is basically the same as the preparation of long-chain alkyl polyphenylene ether in Example 1, except that the reaction time is 10 h. After the reaction is completed, long-chain alkyl polyphenylene ether A2 is obtained, wherein the polymerization amount m+n of more than 60% of the components is 10-20.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 h, mix well, and obtain resin composition C2.

4. Preparation of laminates

The resin composition was replaced by resin composition C2, and the others were the same as in Example 1 to obtain a laminate D2.

Example 3

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation of long-chain alkyl polyphenylene ether is basically the same as that in Example 1, except that the reaction time is 14 h. After the reaction is completed, the long-chain alkyl polyphenylene ether A3 is obtained, wherein the polymerization amount m+n of more than 60% of the components is 25-35.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition C3.

4. Preparation of laminates

The resin composition was replaced by resin composition C3, and the others were the same as in Example 1 to obtain a laminate D3.

Example 4

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition C4.

4. Preparation of laminates

The resin composition was replaced by resin composition C4, and the others were the same as in Example 1 to obtain a laminate D4.

Example 5

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition C5.

4. Preparation of laminates

The resin composition was replaced by resin composition C5, and the others were the same as in Example 1 to obtain a laminate D5.

Example 6

1. Preparation of precursor

Add 57.3 g of 2,6-dimethylphenol and 40.21 g of tricosanone (Tricosanone) into a 500 mL four-neck flask, control the reflux condensation temperature at 0 °C, and slowly add the catalyst (3 g of trifluoromethane sulfur acid and 1 g sulfuric acid), the reaction temperature was controlled at 80 °C, and the reaction time was 12 h. After the reaction was completed, the product was dissolved with ether, neutralized and extracted with saturated aqueous sodium bicarbonate solution, and the organic layer was kept, and extracted with deionized water until the pH was 5~6. Concentrate the organic layer, add methanol solution (the volume ratio of deionized water to methanol is 1:3), mix and put it in a refrigerator at 4 °C to crystallize, and filter the precipitated product to obtain the precursor X2, the product is about 51.755g, and the product The rate is 77%.

（式VI）。 The structure of the precursor X2 is shown in formula VI, and the relative molecular mass is 564.92426.

(Formula VI).

2. Preparation of long chain alkyl polyphenylene ether

（式VII）。 The method for preparing long-chain alkyl polyphenylene ether is basically the same as that in Example 1, except that the precursor X1 is replaced by the precursor X2, the amount of the precursor X2 added is 370 g, and the reaction is stirred at 35 °C for 1-3 hours. After the reaction is completed, long-chain alkyl polyphenylene ether A6 is obtained, the structure of which is shown in formula VII.

(Formula VII).

60% of the long-chain alkyl polyphenylene ethers in A6 are long-chain polyphenylene ethers with m+n=24~28 and molecular weight Mn=3565~3805. The product is an orange powder, which has good solubility in solvents such as benzene, ketones, amides, and pyridine. The infrared spectrum of the product is shown in Figure 2.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature, mix evenly, and obtain resin composition C6.

4. Preparation of laminates

The resin composition was replaced by resin composition C6, and the others were the same as in Example 1 to obtain a laminate D6.

Example 7

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 h, mix well, and obtain resin composition C7.

4. Preparation of laminates

The resin composition was replaced by resin composition C7, and the others were the same as in Example 1 to obtain a laminate D7.

Example 8

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition C8.

4. Preparation of laminates

The resin composition was replaced by resin composition C8, and the others were the same as in Example 1 to obtain a laminate D8.

Example 9

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 hours, mix well, and obtain resin composition C9.

4. Preparation of laminates

The resin composition was replaced by resin composition C9, and the others were the same as in Example 1 to obtain a laminate D9.

Example 10

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 1, put each raw material in a stirrer, stir at room temperature for 2-4 h, mix well, and obtain resin composition C10.

4. Preparation of laminates

The resin composition was replaced by resin composition C10, and the other was the same as in Example 1 to obtain a laminate D10.

Comparative example 1

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation of the long-chain alkyl polyphenylene ether is basically the same as that in Example 1, except that the stirring reaction time at 50 °C is 8 h. After the reaction is completed, the long-chain alkyl polyphenylene ether B1 is obtained, and the reactivity is reduced, wherein more than 50% of the polymerization amount m+n<10.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 2, put each raw material in a stirrer, stir at room temperature, mix evenly, and obtain resin composition E1.

4. Preparation of laminates

The resin composition was replaced by resin composition E1, and the others were the same as in Example 1 to obtain laminate F1.

Comparative example 2

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation of long-chain alkyl polyphenylene ether is basically the same as that in Example 1, except that the stirring reaction time at 70° C. is 16 h. After the reaction is completed, the long-chain alkyl polyphenylene ether B2 is obtained, and the reactivity is too high, wherein more than 50% of the polymerization amount m+n=40~60.

3. Preparation of resin composition

Weigh each raw material according to the ratio of raw materials in Table 2, put each raw material in a stirrer, stir at room temperature, mix evenly, and obtain resin composition E2.

4. Preparation of laminates

The resin composition was replaced by the resin composition E2, and the others were the same as in Example 1 to obtain the laminate F2.

Comparative example 3

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Each raw material was weighed according to the ratio of raw materials in Table 2, each raw material was placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E3.

4. Preparation of laminates

The resin composition was replaced by the resin composition E3, and the others were the same as in Example 1 to obtain a laminate F3.

Comparative example 4

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Each raw material was weighed according to the ratio of raw materials in Table 2, each raw material was placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E4.

4. Preparation of laminates

The resin composition was replaced by resin composition E4, and the other was the same as in Example 1 to obtain laminate F4.

Comparative example 5

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Each raw material was weighed according to the ratio of raw materials in Table 2, each raw material was placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E5.

4. Preparation of laminates

The resin composition was replaced by the resin composition E5, and the others were the same as in Example 1 to obtain a laminate F5.

Comparative example 6

1. Preparation of precursor

The preparation method of the precursor is the same as in Example 1.

2. Preparation of long chain alkyl polyphenylene ether

The preparation method of long-chain alkyl polyphenylene ether is the same as that in Example 1.

3. Preparation of resin composition

Each raw material was weighed according to the ratio of raw materials in Table 2, each raw material was placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E6.

4. Preparation of laminates

The resin composition was replaced by resin composition E6, and the other was the same as in Example 1 to obtain laminate F6.

Comparative example 7

1. Short chain polyphenylene ether

（式VIII）。 Dimethyl polyphenylene ether (B7) of model SA90 purchased from SABIC Company, the structure of polyphenylene ether B7 is shown in the following formula VIII, and the number average molecular weight Mn is about 1600.

(Formula VIII).

2. Preparation of resin composition

Each raw material was weighed according to the ratio of raw materials in Table 2, each raw material was placed in a stirrer, stirred at room temperature, and mixed uniformly to obtain resin composition E7.

3. Preparation of laminates

The resin composition was replaced by resin composition E7, and the other was the same as in Example 1 to obtain a laminate F7.

The raw materials and proportioning ratio of the epoxy resin composition of the embodiment are shown in Table 1, and the raw materials and proportioning ratio of the epoxy resin composition of the comparative example are shown in Table 2. [Table 1] Raw materials and proportioning (parts by weight) of the epoxy resin composition of the embodiment resin composition C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 epoxy resin 100 100 100 100 100 100 100 100 100 100 Long chain alkyl polyphenylene ether A1 (C10) m+n=24~27 50 / / 20 60 / 50 50 20 50 Long chain alkyl polyphenylene ether A2 (C10) m+n=10~20 / 50 / / / / / / / / Long chain alkyl polyphenylene ether A3 (C10) m+n=25~35 / / 50 / / / / / / / Long chain alkyl polyphenylene ether A6 (C23) m+n=24~28 / / / / / 50 / / / / Bismaleimide Resin 90 90 90 90 90 90 80 100 80 90 hardener 60 60 60 60 60 60 60 60 60 60 2E4MI 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 silicon dioxide 30 30 30 30 30 30 30 30 30 - Silane coupling agent 1 1 1 1 1 1 1 1 1 - Toluene 150 150 150 150 150 150 150 150 150 150

Among them, brominated bisphenol A epoxy resin adopts Taiwan Changchun Chemical BEB530A80, bismaleimide resin adopts Yamato Kasei BMI 5100, hardener adopts diaminodiphenylsulfone, and silane coupling agent adopts Shin-Etsu Chemistry KBM-974H. [Table 2] Raw materials and proportioning (parts by weight) of the epoxy resin composition of the comparative example resin composition E1 E2 E3 E4 E5 E6 E7 epoxy resin 100 100 100 100 100 100 100 Long chain alkyl polyphenylene ether A1 (C10) m+n=24~27 / / 10 70 50 50 / Long chain alkyl polyphenylene ether B1 (C10) m+n<10 50 / / / / / / Long chain alkyl polyphenylene ether B2 (C10) m+n=40~60 / 50 / / / / / Short chain alkyl polyphenylene ether B7 (C3) / / / / / / 50 Bismaleimide Resin 90 90 90 90 70 110 90 hardener 60 60 60 60 60 60 60 2E4MI 0.1 0.1 0.1 0.1 0.1 0.1 0.1 silicon dioxide 30 30 30 30 30 30 30 Silane coupling agent 1 1 1 1 1 1 1 Toluene 150 150 150 150 150 150 150

Among them, brominated bisphenol A epoxy resin adopts Taiwan Changchun Chemical BEB530A80, bismaleimide resin adopts Yamato Kasei BMI 5100, hardener adopts diaminodiphenylsulfone, and silane coupling agent adopts Shin-Etsu Chemistry KBM-974H.

Experimental example 1

Perform performance tests on the laminates in the examples and comparisons. The test items include glass transition temperature (Tg), dielectric constant, dissipation factor, water absorption, thermal expansion coefficient, expansion rate in the Z-axis direction, thermal decomposition temperature, toughness and resistance. Flammability, etc., the test method is as follows:

(1) Differential scanning calorimetry (DSC) analysis: Differential scanning calorimeter (model: DSC 7) of Perkin-Elmer Company.

(2) Colloidal chromatography (gel permeation chromatography, GPC) analysis: Waters company's colloidal chromatography analyzer (model: waters 600).

(3) Glass transition temperature test: The glass transition temperature (Tg) was measured using a dynamic mechanical analyzer (DMA). The test specification for the glass transition temperature is the IPC-TM-650.2.4.25C and 24C detection methods of the Institute for Interconnecting and Packaging Electronic Circuits (IPC).

(4) Measurement of dielectric constant and dissipation factor: According to ASTM D150 specification, at a working frequency of 1 megahertz (GHz), the dielectric constant (dielectric constant, Dk) and dissipation factor (dissipation factor, Df) were calculated.

(5) Water absorption test: carry out the pressure cooker test (PCT) test, place the laminate in a pressure vessel, and test it under the environment of 121 ℃, saturated humidity (100% R.H.) and 1.2 atmospheric pressure for 2 hours. High humidity resistance of laminates.

(6) Thermal expansion coefficient test and Z-axis expansion rate: Measured with a thermal expansion analyzer (model TA 2940) of TA instrument company, the measurement condition is a temperature rise of 5 °C per minute in the temperature range from 50 °C to 260 °C Raise the temperature at a high rate, and measure the thermal expansion coefficient in the thickness direction (Z-axis direction) and the expansion rate in the Z-axis direction of the sample (a laminate with a size of 3 mm2).

(7) Thermal decomposition temperature test: use a thermogravimetric analyzer (thermogravimetric analyzer, TGA) to measure the temperature when the mass is reduced by 5% compared with the initial mass, which is the thermal decomposition temperature.

(8) Toughness test: Place the laminate flat on a plane fixture, use a cross-shaped metal fixture to contact the surface of the laminate vertically, apply vertical pressure, remove the cross fixture, and observe the shape of the cross on the laminate Check the surface of the laminate, if there is no white crease, it is judged as good, if there is a little white line, it is normal, and if there is crack or break, it is bad.

(9) Tear strength test: Tear strength refers to the adhesion of copper foil to the substrate, usually the copper foil per inch (25.4 mm) width is torn vertically from the board surface, with the required force The size to express the strength of adhesion. MIL-P-55110E stipulates that the pass standard for substrates with 1 oz copper foil is 8 lb/in.

(10) Solder dipping resistance test: After immersing the dried laminated board in a tin soldering bath at 288 ℃ for 10 seconds, repeat the dipping several times to determine the delamination or swelling of the laminated board.

The test results of Examples and Comparative Examples are shown in Table 3 and Table 4 respectively. [Table 3] Properties of Example laminates laminate D1 D2 D3 D4 D5 D6 D7 D8 D9 D10 DSC Tg (℃) 217 216 217 226 216 215 213 218 225 218 Dk (5GHz) 4.24 4.24 4.26 4.25 4.24 4.27 4.25 4.28 4.25 4.22 Df(×10 ³ ) (5GHz) 4.09 4.11 4.08 4.17 4.08 4.20 4.15 4.21 4.12 4.10 Water absorption (%) PCT 6 hours 0.26 0.28 0.25 0.24 0.25 0.23 0.29 0.28 0.23 0.30 Coefficient of thermal expansion (ppm/ ^o C) 27.95 28.11 27.36 33.95 27.5 28.56 29.43 27.35 32.5 35.55 Z-axis expansion (%) 1.58 1.61 1.59 1.7 1.55 1.70 1.85 1.63 1.75 1.92 Thermal decomposition temperature ( ^oC ) 411.7 410.8 413.2 414.2 412.3 417.4 403.6 412.3 412.3 411.9 toughness good good good good good good good generally good good Tear Strength (1oz) (lb/in) 8.9 8.7 9.1 8.5 9.0 8.3 8.7 9.3 8.7 8.7 Solder dip resistance(288 ^o C)(min) >60 >60 >60 >60 >60 >60 >60 >60 >60 >60 [Table 4] Properties of laminated boards of comparative examples laminate F1 F2 F3 F4 F5 F6 F7 DSC Tg (°C) 215 217 228 215 211 223 227 Dk (5GHz) 4.31 4.15 4.39 4.14 4.24 4.25 4.36 Df(×10 ³ ) (5GHz) 4.23 4.01 4.41 4.05 4.17 4.17 4.19 Water absorption (%) PCT2 hours 0.35 0.24 0.22 0.28 0.30 0.28 0.28 Coefficient of thermal expansion (ppm/ ^o C) 28.55 26.36 35.85 26.13 30.07 27.25 41.48 Z-axis expansion (%) 1.89 1.59 1.93 1.55 1.95 1.71 1.83 Thermal decomposition temperature ( ^oC ) 410.1 415.3 418.2 411.3 401.5 412.5 405.2 toughness good inferior good inferior good inferior good Tear Strength (1oz) (lb/in) 8.5 9.3 8.1 9.0 8.7 9.3 8.5 Solder dip resistance(288 ^o C)(min) <60 >60 <60 >60 >60 >60 >60

As can be seen from the above results, the laminates prepared by the resin composition of the present invention (Examples 1 to 10) have better glass transition temperature, water absorption and thermal expansion coefficient and excellent electrical properties (low Dk and Df ). There are defects in the appearance, toughness or structural stability of the laminates of the comparative example, such as the poor dip soldering resistance of the laminates F1 and F3, the poor toughness of the laminates F2, F4, and F6, and the heat resistance of the Tg and thermal decomposition temperature of the laminate F5. The thermal expansion coefficient of the laminate F7 is relatively high, and the structural stability is poor.

Comparing laminates F3, D4, D1, D3 and F4, it can be seen that within a certain range, as the amount of long-chain alkyl polyphenylene ether increases, the Dk and Df of laminates decrease, and the expansion coefficient decreases (dimensional stability Better), the tear strength (adhesion) increases, and the dip soldering resistance becomes better; below or beyond this range, the water absorption of the laminate increases and the toughness deteriorates.

Comparing the laminates F1, D2, D1, D3 and F2, it can be seen that within a certain range, as the polymerization amount m+n increases, the Dk and Df of the laminates decrease, the electrical properties become better, the water absorption decreases, and the expansion coefficient Decrease (dimensional stability becomes better), tear strength (adhesion) increases; beyond this range, the toughness of the laminate becomes worse.

Comparing laminates F5, D7, D1, D8 and F6, it can be seen that within a certain range, as the amount of bismaleimide resin increases, the expansion coefficient decreases (the dimensional stability becomes better), and the tear strength ( Adhesion) is improved; beyond this range, the toughness of the laminate becomes worse.

Comparing the laminates F7, D1 and D6, it can be seen that as the alkyl chain of the long-chain alkyl polyphenylene ether grows, the water absorption of the laminate decreases and the expansion coefficient decreases (the dimensional stability becomes better), and the Dk and DF values decrease, the thermal decomposition temperature increases.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Fig. 1 is the infrared spectrogram of long-chain alkyl polyphenylene ether A1 in Example 1. Fig. 2 is the infrared spectrogram of long-chain alkyl polyphenylene ether A6 in Example 2.

Claims (10)

A long-chain alkyl polyphenylene ether resin composition, which includes the following raw materials in parts by weight: 100 parts of epoxy resin, 20-60 parts of long-chain alkyl polyphenylene ether, and 80-100 parts of bismaleimide resin , 40-80 parts of hardener; the structure of the long-chain alkyl polyphenylene ether is shown in formula I:

Formula I wherein, R ₁ -CR ₂ is a C8~C25 alkyl group, m+n=10~40, and the number average molecular weight Mn is 1500~6000. The long-chain alkyl polyphenylene ether resin composition as claimed in claim 1, wherein the epoxy resin is selected from: brominated bisphenol A epoxy resin, bisphenol A novolac epoxy resin, bisphenol F type One or more of novolak epoxy resin and phosphorus-containing epoxy resin. The long-chain alkyl polyphenylene ether resin composition as claimed in item 1, wherein the bismaleimide resin is selected from: 4,4'-diphenylmethane bismaleimide, bismaleimide Imide toluene, diethyl bismaleimide toluene, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4, 4'-Diphenylmethane bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylphenylmaleimide One or more of imine, 2,6-dimethylbenzmaleimide, N-phenylmaleimide, and maleimide containing aliphatic long-chain structure. The long-chain alkyl polyphenylene ether resin composition according to Claim 1, wherein the hardener is selected from one or both of diamino-diphenylsulfone and amino-triazine phenolic resins. The long-chain alkyl polyphenylene ether resin composition according to claim 1, further comprising 130-170 parts of solvent and 30-35 parts of functional additives. The long-chain alkyl polyphenylene ether resin composition as claimed in item 2, wherein the solvent is selected from: toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, butanone, acetone, xylene, methyl One or more of isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; the functional additives are selected from: fillers , flame retardant, hardening accelerator, dispersant, toughening agent in one or two or more. The long-chain alkyl polyphenylene ether resin composition as described in any one of claim items 1 to 6, wherein, the R ₁ is a C9 or C11 long-chain alkyl group, and the R ₂ is hydrogen or a C11 long-chain alkane base; m+n=24~35 of the long-chain alkyl polyphenylene ether, and the number average molecular weight Mn is 3300~4000. The long-chain alkyl polyphenylene ether resin composition as claimed in item 1, wherein the long-chain alkyl polyphenylene ether tree is prepared by the following method: S1. Using C8~C25 alkyl ketones and 2,6-dimethylphenol as raw materials, using trifluoromethanesulfonic acid and sulfuric acid as catalysts, react to obtain precursors; S2. Mix the precursor, metal catalyst, dimethylbutylamine and solvent to obtain a pre-reaction solution; dissolve 2,6-dimethylphenol in the solvent to obtain a 2,6-dimethylphenol solution; The reaction solution is mixed with the 2,6-dimethylphenol solution to react to obtain long-chain alkyl polyphenylene ether. A prepreg, wherein it is prepared from raw materials including the long-chain alkyl polyphenylene ether resin composition described in any one of Claims 1 to 8. An application of the long-chain alkyl polyphenylene ether resin composition as described in any one of claim items 1 to 8 or the prepreg as described in claim item 9 in the preparation of laminated boards.

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